CN114181382A - Unsaturated fatty diacid-based polyester polyol and synthetic method thereof - Google Patents
Unsaturated fatty diacid-based polyester polyol and synthetic method thereof Download PDFInfo
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- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G63/00—Macromolecular compounds obtained by reactions forming a carboxylic ester link in the main chain of the macromolecule
- C08G63/66—Polyesters containing oxygen in the form of ether groups
- C08G63/668—Polyesters containing oxygen in the form of ether groups derived from polycarboxylic acids and polyhydroxy compounds
- C08G63/676—Polyesters containing oxygen in the form of ether groups derived from polycarboxylic acids and polyhydroxy compounds in which at least one of the two components contains aliphatic unsaturation
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- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G63/00—Macromolecular compounds obtained by reactions forming a carboxylic ester link in the main chain of the macromolecule
- C08G63/02—Polyesters derived from hydroxycarboxylic acids or from polycarboxylic acids and polyhydroxy compounds
- C08G63/12—Polyesters derived from hydroxycarboxylic acids or from polycarboxylic acids and polyhydroxy compounds derived from polycarboxylic acids and polyhydroxy compounds
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Abstract
The invention relates to a synthetic method of unsaturated fatty diacid polyester polyol, which comprises the following steps: (1) under the action of a solid acid esterification catalyst, carrying out esterification reaction on unsaturated fatty diacid and methanol to generate unsaturated fatty diacid dimethyl ester; (2) after the esterification reaction is finished, separating unsaturated fatty diacid dimethyl ester from a solid acid esterification catalyst, sending the mixture into a polyol solution added with an ester exchange catalyst, stirring and mixing the mixture evenly, and heating the mixture to perform an ester exchange reaction to generate diacid diol ester; (3) after the ester exchange reaction is finished, continuously heating and carrying out polycondensation reaction to obtain the target product. Compared with the prior art, the polyurethane obtained when the polyester polyol is used for synthesizing the polyurethane has temperature sensitivity, rebound resilience and the like.
Description
Technical Field
The invention belongs to the technical field of fatty acid-based polyester polyol synthesis, and relates to unsaturated fatty dibasic acid-based polyester polyol and a synthesis method thereof.
Background
Polymer polyol is one of important raw materials in the polyurethane industry, and in addition to polyether polyol, polyester polyol imparts unique properties to polyurethane, is an important synthetic raw material in the polyurethane field and the like, and plays an important role in the chemical industry.
Along with the improvement of the quality of social life, higher requirements are put forward on the service performance of polyurethane, for example, the polyurethane can be softened above a certain service temperature, and when the temperature is lower than a certain service temperature, the polyurethane foam is hardened from soft, so that the polyurethane foam has the characteristic of good temperature sensitivity. Meanwhile, the polyurethane is required to be capable of being restored to the original form slowly after being extruded and deformed, and has a good rebound resilience characteristic. It is important to combine these two properties of polyurethane, which is closely related to the raw materials for preparing polyurethane, and therefore the present invention is based on this.
Disclosure of Invention
The invention aims to provide unsaturated fatty diacid polyester polyol and a synthesis method thereof, wherein polyurethane obtained when the unsaturated fatty diacid polyester polyol is used for polyurethane synthesis has temperature sensitivity, rebound resilience and the like.
The purpose of the invention can be realized by the following technical scheme:
one of the technical schemes of the invention provides a method for synthesizing unsaturated fatty diacid polyester polyol, which comprises the following steps:
(1) under the action of a solid acid esterification catalyst, carrying out esterification reaction on unsaturated fatty diacid and methanol to generate unsaturated fatty diacid dimethyl ester;
(2) after the esterification reaction is finished, separating unsaturated fatty diacid dimethyl ester from a solid acid esterification catalyst, sending the mixture into a polyol solution added with an ester exchange catalyst, stirring and mixing the mixture evenly, and heating the mixture to perform an ester exchange reaction to generate diacid diol ester;
(3) after the ester exchange reaction is finished, continuously heating and carrying out polycondensation reaction to obtain the target product.
Further, in the step (1), the unsaturated fatty diacid is one or a mixture of more of 2-pentene-1, 5-diacid, 3-methyl-2-pentene-1, 5-diacid, 2-hexene-1, 6-diacid and 2, 4-hexadiene-1, 6-adipic acid. In order to obtain better temperature sensitivity and rebound resilience performance of the polyurethane, saturated dibasic acid such as glutaric acid, adipic acid or pimelic acid and the like is added into a system during polymerization so as to adjust the content and distribution of double bonds on a polyester chain. The proportion of the saturated dibasic acids such as glutaric acid, adipic acid or pimelic acid is generally not less than 40% by moles of the total molar amount of all dibasic acids.
Further, in the step (1), the solid acid esterification catalyst is perfluorosulfonic acid resin (Nafion-H) or sulfated metal oxide, wherein the sulfated metal oxide is SO4 2-/Al2O3、SO4 2-/ZrO2、SO4 2-/TiO2、SO4 2-/WO3、SO4 2-/W20O58、SO4 2-/NbxOyX is 1 or 2; y is 1,2, 3, 5. Nafion-H is preferred.
Further, in the step (1), the amount of the solid acid esterification catalyst is 0.1-8% by mass of the unsaturated fatty diacid, preferably 0.5-5% by mass of the unsaturated fatty diacid.
Further, in the step (1), the amount of the methanol is 100 to 160 percent of the molar amount of the unsaturated fatty diacid, and is about 130 percent optionally.
Further, in the step (1), the temperature of the esterification reaction is 50-100 ℃, preferably 60-85 ℃, and the time is 1-8.5 h, preferably 3-6 h.
Further, in the step (1), the dibasic acid dimethyl ester obtained by the esterification reaction comprises: dimethyl 2-pentene-1, 5-dioate, dimethyl 3-methyl-2-pentene-1, 5-dioate, dimethyl 2-hexene-1, 6-dioate, dimethyl 2, 4-hexadiene-1, 6-adipate, dimethyl glutarate, dimethyl adipate or dimethyl pimelate, and the like.
Further, in the step (2), the polyol is one or a mixture of more of ethylene glycol, diethylene glycol, triethylene glycol, 1, 2-propylene glycol, 1, 3-propylene glycol, 1, 2-butylene glycol and 1, 4-butylene glycol, and the use of the diol is one of the factors for obtaining the polyurethane with the temperature sensitivity and the rebound resilience.
Further, in the step (2), the transesterification catalyst is Sb2O3Antimony acetate, GeO2N-butyl titanate, isopropyl titanate, TiO2/SiO2One or more of the compounds are combined, the addition amount of the compound is 5ppm to 225ppm of the total mass of the unsaturated fatty diacid and the dihydric alcohol, and the preferred amount is 10ppm to 150 ppm. Here, the same applies to the polycondensation reaction as the catalyst.
Further, in the step (2), the molar ratio of the polyhydric alcohol to the unsaturated fatty diacid dimethyl ester is 1.25: 1-1.05: 1.
Further, in the step (2), the ester exchange reaction process is to add dimethyl diacid into a reactor containing glycol and an ester exchange catalyst solution, gradually raise the temperature to 115-190 ℃ while stirring, mix and dissolve, and perform ester exchange reaction for 1-10 hours, wherein the generated methanol is separated and removed by a rectifying tower arranged at the top of the reaction kettle, the preferred temperature range is 110-185 ℃, and the preferred reaction time is 5-8 hours. When substantially no methanol is formed, the polycondensation process is entered.
Further, in the step (3), the temperature of the polycondensation reaction is 220-260 ℃, preferably 230-250 ℃, in the polycondensation process, a gradual heating method is adopted to control the reaction temperature, the heating speed is controlled to be 0.5-2 ℃/min, the constant temperature is maintained for 2-10 h after the temperature is raised to the specified temperature, and preferably the time range is 4-8 h. The diol removed by the reaction is cooled by a condenser arranged at the top of the reactor and then collected, separated and recycled.
Further, a stabilizer is added to the whole reaction system to prevent the unsaturated double bond from being destroyed, the stabilizer is hydroquinone, p-hydroxyanisole, 2, 5-di-tert-butylhydroquinone, 2-tert-butylhydroquinone, p-benzoquinone, methylhydroquinone, 2,6, 6-tetramethyl-4-hydroxypiperidine nitroxide radical (also referred to as ZM-701), and one of them may be added or a plurality of them may be mixed for use. The addition amount is 0.03-1.2% of the mass of the unsaturated raw materials in the reaction system, and the preferable dosage is 0.1-1.0%.
In order to prevent the adverse effect of oxygen in the air in the polymerization process, N needs to be introduced into the system in the process2The reaction is maintained in the substantial absence of oxygen. In the polycondensation stage, it is necessary to work under a relatively high vacuum, typically at a pressure of less than 2kPa, in order to increase the molecular weight of the polyester polyol. N may also be introduced into the system2Using N2The gas flow carries the small analytes produced out of the system to increase molecular weight.
The second technical scheme of the invention provides unsaturated fatty diacid polyester polyol which is synthesized by adopting any one of the synthesis methods.
Detailed Description
The present invention will be described in detail with reference to specific examples. The present embodiment is implemented on the premise of the technical solution of the present invention, and a detailed implementation manner and a specific operation process are given, but the scope of the present invention is not limited to the following embodiments.
In the following examples, TiO2/SiO2Composite, catalyst SO4 2-/TiO2The isosulfated metal oxides are commercially available. Otherwise, unless otherwise specified, all the conventional commercial raw materials or conventional processing techniques are used in the art.
Example 1
960g of methanol, 300g of toluene (water used as entrainer to form an azeotrope with the water of reaction, removed from the top of the reactor, and after water separation, the toluene was returned to the reactor) and 1.18g of hydroquinone were charged to the reactor and heated to 45 ℃ with stirring. Adding 54.95g of catalyst Nafion-H, 633.6g of 2-hexene-1, 6-diacid and 817.6g of adipic acid into a reactor, stirring, dissolving and heating at the same time, heating to 90 ℃ within 15min, reacting dibasic acid with methanol during heating, allowing water generated by reaction to leave the reactor through an azeotrope formed by the water and toluene and part of methanol, entering a rectifying tower arranged at the top of the reactor for separation, discharging methanol from the top of the tower and refluxing to the reactor, distilling the azeotrope of toluene and water from the bottom of the tower and entering a water separator, removing water, and refluxing the toluene to the reactor. The reaction was continued at 90 ℃ for 4.5h until no water was formed. Separating to remove the solid catalyst, heating the liquid material to 115 ℃, and distilling to remove the toluene in the system.
Adding a liquid methyl diacid product obtained by the esterification reaction into another reactor while the liquid methyl diacid product is hot, adding 1636.5g of triethylene glycol into the reactor under the stirring condition, adding 447.7mg of catalyst of antimony acetate, heating to 180 ℃, carrying out ester exchange reaction for 8h at 180 ℃, and separating and removing generated methanol from a distillation tower at the top of the reactor. When no methanol is generated, the oligomer of diacid and diol is obtained.
Vacuumizing the reactor, keeping the pressure of the reactor lower than 2kPa, gradually heating to 230 ℃ at the speed of 2 ℃/min, and reacting for 6h at constant temperature. Slowly introducing N into the reactor2And simultaneously closing the vacuum system, opening a discharge valve after the reactor is heated to normal pressure, and discharging the materials to obtain the required polyester polyol. Sampling and analyzing acid ester, hydroxyl value, iodine value and molecular weight. The acid ester has a hydroxyl value of 70.52mgKOH/g, an iodine value of 0.103, a molecular weight of 7583g/mol and a temperature sensitivity index of 5.7 of 1.506 mgKOH/g.
Example 2
1280g of methanol, 300g of toluene and 1.178g of hydroquinone are introduced into a reactor, and the temperature is raised to 45 ℃ with stirring. 25.73g of catalyst SO were charged to the reactor4 2-/TiO2539.6g of 2, 4-hexadiene-1, 6-adipic acid and 992g of pimelic acid are added, stirring and dissolving are carried out, the temperature is raised to 85 ℃ within 15min, the dibasic acid and methanol start to react in the temperature raising process, water generated by the reaction leaves the reactor through an azeotrope formed by the dibasic acid and the toluene and part of the methanol, the water enters a rectifying tower arranged at the top of the reactor for separation, the methanol slips out from the top of the tower and flows back to the reactor, the azeotrope of the toluene and the water is distilled out from the bottom of the tower and enters a water separator, the water is separated, and the toluene flows back to the reactor. The reaction was continued at 85 ℃ for 4h until no water was formed. Separation of solid catalystHeating the liquid material to 115 deg.c, and distilling to eliminate toluene.
Adding a liquid methyl diacid product obtained in the esterification reaction into another reactor while the liquid methyl diacid product is hot, adding 666.5g of ethylene glycol into the reactor under the stirring condition, adding 274.7mg of catalyst isopropyl titanate, heating to 130 ℃, carrying out ester exchange reaction for 6h at 130 ℃, and separating and removing generated methanol from a distillation tower at the top of the reactor. When no methanol is generated, the oligomer of diacid and diol is obtained.
Vacuumizing the reactor, keeping the pressure of the reactor lower than 2kPa, gradually heating to 240 ℃ at the speed of 2 ℃/min, and reacting for 2h at constant temperature. Slowly introducing N into the reactor2And simultaneously closing the vacuum system, opening a discharge valve after the reactor is heated to normal pressure, and discharging the materials to obtain the required polyester polyol. Sampling and analyzing acid ester, hydroxyl value, iodine value and molecular weight. The acid ester has a hydroxyl value of 60.36mgKOH/g, an iodine value of 0.092, a molecular weight of 8817g/mol and a temperature sensitivity index of 8.5 and is 1.950 mgKOH/g.
Example 3
1760g of methanol, 300g of toluene and 3.432g of p-benzoquinone were charged into the reactor, and the temperature was raised to 45 ℃ with stirring. 98.48g of catalyst SO were charged to the reactor4 2-/Al2O3286g of 2-pentene-1, 5-diacid and 1248g of pimelic acid are added, stirring and dissolving are carried out, the temperature is raised at the same time, the temperature is raised to 70 ℃ within 15min, in the process of temperature rise, dibasic acid and methanol start to react, water generated by reaction leaves a reactor through an azeotrope formed by the dibasic acid and methylbenzene and part of the methanol, the water enters a rectifying tower arranged at the top of the reactor for separation, the methanol slides out from the top of the tower and flows back to the reactor, the azeotrope of the methylbenzene and the water is distilled out from the bottom of the tower, the water is separated, and the methylbenzene flows back to the reactor. The reaction was continued at 70 ℃ for 6h until no water had formed. Separating to remove the solid catalyst, heating the liquid material to 115 ℃, and distilling to remove the toluene in the system.
Adding the liquid product of the methyl diacid obtained from the esterification reaction into another reactor while the liquid product is hot, adding 1093.5g of 1, 2-butanediol into the reactor under the condition of stirring, and adding 105.1mg of catalyst Sb2O3Heating to 16 deg.CThe transesterification was carried out at 0 ℃ for 1h at 160 ℃ and the methanol formed was separated off from the distillation column at the top of the reactor. When no methanol is generated, the oligomer of diacid and diol is obtained.
Vacuumizing the reactor, keeping the pressure of the reactor lower than 2kPa, gradually heating to 240 ℃ at the speed of 2 ℃/min, and reacting for 6h at constant temperature. Slowly introducing N into the reactor2And simultaneously closing the vacuum system, opening a discharge valve after the reactor is heated to normal pressure, and discharging the materials to obtain the required polyester polyol. Sampling and analyzing acid ester, hydroxyl value, iodine value and molecular weight. The acid ester has the advantages of 0.766mgKOH/g, 40.04mgKOH/g hydroxyl value, 0.131 iodine value, 4500g/mol molecular weight and 7.6 temperature sensitivity index.
Example 4
2560g of methanol, 300g of toluene and 1.808g of methylhydroquinone are introduced into the reactor, and the temperature is raised to 45 ℃ with stirring. 15.40g of catalyst SO were charged to the reactor4 2-/W20O58187.2g of 2-hexene-1, 6-diacid and 1148.4g of glutaric acid are added, stirring and dissolving are carried out, the temperature is raised simultaneously, the temperature is raised to 55 ℃ within 15min, during the temperature raising process, dibasic acid and methanol start to react, water generated by the reaction leaves the reactor through an azeotrope formed by the dibasic acid and toluene and part of methanol, the water enters a rectifying tower arranged at the top of the reactor for separation, the methanol slides out from the top of the tower and flows back to the reactor, the azeotrope of the toluene and water is distilled out from the bottom of the tower, the water is separated, and the toluene flows back to the reactor. The reaction was continued at a constant temperature of 55 ℃ for 2.5h until no water was formed. Separating to remove the solid catalyst, heating the liquid material to 115 ℃, and distilling to remove the toluene in the system.
Adding the liquid product of the methyl diacid obtained from the esterification reaction into another reactor while the liquid product is hot, adding 1234.9g of diethylene glycol into the reactor under the condition of stirring, and adding 475.5mg of catalyst GeO2The temperature is raised to 145 ℃, the ester exchange reaction is carried out for 5h at 145 ℃, and the generated methanol is separated and removed from a distillation tower at the top of the reactor. When no methanol is generated, the oligomer of diacid and diol is obtained.
Vacuumizing the reactor, keeping the pressure of the reactor lower than 2kPa, gradually heating to 240 ℃ at the speed of 2 ℃/min, and keeping the temperature constantAnd reacting for 6 h. Slowly introducing N into the reactor2And simultaneously closing the vacuum system, opening a discharge valve after the reactor is heated to normal pressure, and discharging the materials to obtain the required polyester polyol. Sampling and analyzing acid ester, hydroxyl value, iodine value and molecular weight. The acid ester was 2.690mgKOH/g, hydroxyl value 52.74mgKOH/g, iodine value 0.147, molecular weight 3267g/mol, temperature sensitivity index 4.8.
Example 5
640g of methanol, 300g of toluene and 8.50g of 2-tert-butylhydroquinone were charged into a reactor, and the temperature was raised to 45 ℃ with stirring. 76.61g of catalyst SO was charged to the reactor4 2-/NbxOy1300g of 2-pentene-1, 5-diacid is added, stirring and dissolving are carried out, temperature rising is carried out simultaneously, the temperature rising is carried out within 15min, binary acid and methanol start to react in the temperature rising process, water generated in the reaction leaves a reactor through an azeotrope formed by the binary acid and toluene and part of methanol, enters a rectifying tower arranged at the top of the reactor for separation, the methanol slides out from the tower top and flows back to the reactor, the azeotrope of the toluene and the water is distilled out from the tower bottom, enters a water separator, moisture is removed, and the toluene flows back to the reactor. The reaction was continued at 100 ℃ for 3.5h until no water was formed. Separating to remove the solid catalyst, heating the liquid material to 115 ℃, and distilling to remove the toluene in the system.
Adding a liquid methyl diacid product obtained by the esterification reaction into another reactor while the liquid methyl diacid product is hot, adding 756.4g of ethylene glycol into the reactor under the stirring condition, adding 339.3mg of antimony acetate serving as a catalyst, heating to 155 ℃, carrying out ester exchange reaction for 3h at 155 ℃, and separating and removing generated methanol from a distillation tower at the top of the reactor. When no methanol is generated, the oligomer of diacid and diol is obtained.
Vacuumizing the reactor, keeping the pressure of the reactor lower than 2kPa, gradually heating to 220 ℃ at the speed of 2 ℃/min, and reacting for 4h at constant temperature. Slowly introducing N into the reactor2And simultaneously closing the vacuum system, opening a discharge valve after the reactor is heated to normal pressure, and discharging the materials to obtain the required polyester polyol. Sampling and analyzing acid ester, hydroxyl value, iodine value and molecular weight. The acid ester has a hydroxyl value of 73.06mgKOH/g, an iodine value of 0.125, a molecular weight of 10050g/mol and a temperature of 1.062mgKOH/gThe degree sensitivity index is 7.9.
Example 6
3040g of methanol, 300g of toluene and 1.25g of p-benzoquinone were charged into a reactor, and the temperature was raised to 45 ℃ with stirring. 107.28g of catalyst SO were added to the reactor4 2-/ZrO2298.2g of 2, 4-hexadiene-1, 6-adipic acid and 1042.8g of glutaric acid are added, stirring and dissolving are carried out, the temperature is raised simultaneously, the temperature is raised to 80 ℃ within 15min, in the process of temperature rise, dibasic acid and methanol start to react, water generated by reaction leaves a reactor through an azeotrope formed by the water and toluene and part of methanol, the water enters a rectifying tower arranged at the top of the reactor for separation, the methanol slips out from the top of the tower and flows back to the reactor, the azeotrope of the toluene and water is distilled out from the bottom of the tower and enters a water separator, water is separated, and the toluene flows back to the reactor. The reaction was continued at 80 ℃ for 8.5h until no water was formed. Separating to remove the solid catalyst, heating the liquid material to 115 ℃, and distilling to remove the toluene in the system.
Adding a liquid methyl diacid product obtained by the esterification reaction into another reactor while the liquid methyl diacid product is hot, adding 944.1g of 1, 2-butanediol into the reactor under the stirring condition, adding 194.2mg of catalyst n-butyl titanate, heating to 165 ℃, carrying out ester exchange reaction for 6h at 165 ℃, and separating and removing generated methanol from a distillation tower at the top of the reactor. When no methanol is generated, the oligomer of diacid and diol is obtained.
Vacuumizing the reactor, keeping the pressure of the reactor lower than 2kPa, gradually heating to 235 ℃ at the speed of 2 ℃/min, and reacting for 3.5h at constant temperature. Slowly introducing N into the reactor2And simultaneously closing the vacuum system, opening a discharge valve after the reactor is heated to normal pressure, and discharging the materials to obtain the required polyester polyol. Sampling and analyzing acid ester, hydroxyl value, iodine value and molecular weight. The acid ester has a hydroxyl value of 55.28mgKOH/g, an iodine value of 0.076, a molecular weight of 6967g/mol and a temperature sensitivity index of 7.3, and is 1.210 mgKOH/g.
Example 7
Into the reactor were charged 1920g of methanol, 300g of toluene and 3.43g of methylhydroquinone, and the temperature was raised to 45 ℃ with stirring. 62.92g of catalyst SO were charged to the reactor4 2-/NbxOy1300g of 3-methyl-2-pentene-1, 5-diacid is added, stirring and dissolving are carried out, the temperature is raised simultaneously, the temperature is raised to 65 ℃ within 15min, in the process of temperature raising, dibasic acid and methanol start to react, water generated in the reaction leaves the reactor through an azeotrope formed by the water and methylbenzene and part of the methanol, the water enters a rectifying tower arranged at the top of the reactor to be separated, the methanol flows out from the top of the tower and flows back to the reactor, the azeotrope of the methylbenzene and the water is distilled out from the bottom of the tower and enters a water separator to separate water, and the methylbenzene flows back to the reactor. The reaction was continued at a constant temperature of 65 ℃ for 1h until no water was formed. Separating to remove the solid catalyst, heating the liquid material to 115 ℃, and distilling to remove the toluene in the system.
Adding the liquid product of the methyl diacid obtained from the esterification reaction into another reactor while the liquid product is hot, adding 858.0g of 1, 3-propanediol into the reactor under the stirring condition, and adding 226.6mg of catalyst Sb2O3The temperature is raised to 170 ℃, the ester exchange reaction is carried out for 9h at the temperature of 170 ℃, and the generated methanol is separated and removed from a distillation tower at the top of the reactor. When no methanol is generated, the oligomer of diacid and diol is obtained.
Vacuumizing the reactor, keeping the pressure of the reactor lower than 2kPa, gradually heating to 250 ℃ at the speed of 2 ℃/min, and reacting for 7h at constant temperature. Slowly introducing N into the reactor2And simultaneously closing the vacuum system, opening a discharge valve after the reactor is heated to normal pressure, and discharging the materials to obtain the required polyester polyol. Sampling and analyzing acid ester, hydroxyl value, iodine value and molecular weight. The acid ester has a hydroxyl value of 37.5mgKOH/g, an iodine value of 0.142, a molecular weight of 6350g/mol and a temperature sensitivity index of 6.0 and is 0.914 mgKOH/g.
Example 8
800g of methanol, 300g of toluene and 0.46g of 2-tert-butylhydroquinone were charged into a reactor, and the temperature was raised to 45 ℃ with stirring. 32.08g of catalyst SO was charged to the reactor4 2-/TiO2Adding 52g of 2-pentene-1, 5-diacid and 1401.6g of adipic acid, stirring for dissolving, heating to 95 ℃ within 15min, reacting dibasic acid with methanol during heating, allowing water generated by reaction to leave a reactor through an azeotrope formed by the dibasic acid and toluene and part of methanol, allowing the water to enter a rectifying tower arranged at the top of the reactor for separation, and adding methanol into the reactorThe mixture is discharged from the tower top and flows back to the reactor, the azeotrope of toluene and water is distilled from the tower bottom and enters a water separator, the water is separated, and the toluene flows back to the reactor. The reaction was continued at a constant temperature of 95 ℃ for 7h until no water was formed. Separating to remove the solid catalyst, heating the liquid material to 115 ℃, and distilling to remove the toluene in the system.
Adding the liquid methyl diacid product obtained from the esterification reaction into another reactor while the liquid methyl diacid product is hot, adding 923.4g of 1, 2-propylene glycol into the reactor under the condition of stirring, and adding 534.8mg of TiO catalyst2/SiO2The temperature is raised to 135 ℃, the ester exchange reaction is carried out for 7h at 135 ℃, and the generated methanol is separated and removed from a distillation tower at the top of the reactor. When no methanol is generated, the oligomer of diacid and diol is obtained.
Vacuumizing the reactor, keeping the pressure of the reactor lower than 2kPa, gradually heating to 260 ℃ at the speed of 2 ℃/min, and reacting for 10 hours at constant temperature. Slowly introducing N into the reactor2And simultaneously closing the vacuum system, opening a discharge valve after the reactor is heated to normal pressure, and discharging the materials to obtain the required polyester polyol. Sampling and analyzing acid ester, hydroxyl value, iodine value and molecular weight. The acid ester has a hydroxyl value of 47.66mgKOH/g, an iodine value of 0.081, a molecular weight of 5117g/mol and a temperature sensitivity index of 9.4.
Example 9
1440g of methanol, 300g of toluene and 3.46g of 2, 5-di-tert-butylhydroquinone were introduced into a reactor and the temperature was raised to 45 ℃ with stirring. 50.96g of catalyst SO were added to the reactor4 2-/Al2O3331.2g of 2-hexene-1, 6-diacid and 1232g of pimelic acid are added, stirring and dissolving are carried out, the temperature is raised simultaneously, the temperature is raised to 75 ℃ within 15min, during the temperature raising process, dibasic acid and methanol start to react, water generated by the reaction leaves a reactor through an azeotrope formed by the dibasic acid and toluene and part of methanol, the water enters a rectifying tower arranged at the top of the reactor for separation, the methanol slips out from the top of the tower and flows back to the reactor, the azeotrope of the toluene and water is distilled out from the bottom of the tower, the water is separated, and the toluene flows back to the reactor. The reaction was continued at 75 ℃ for 1.5h until no water was formed. Separating to remove solid catalyst, heating liquid material to 115 deg.C, and distilling to remove solidToluene in the series.
Adding a liquid methyl diacid product obtained in the esterification reaction into another reactor while the liquid methyl diacid product is hot, adding 740.9g of ethylene glycol into the reactor under the stirring condition, adding 207.4mg of catalyst isopropyl titanate, heating to 175 ℃, carrying out ester exchange reaction for 3h at 175 ℃, and separating and removing generated methanol from a distillation tower at the top of the reactor. When no methanol is generated, the oligomer of diacid and diol is obtained.
Vacuumizing the reactor, keeping the pressure of the reactor lower than 2kPa, gradually heating to 250 ℃ at the speed of 2 ℃/min, and reacting for 8 hours at constant temperature. Slowly introducing N into the reactor2And simultaneously closing the vacuum system, opening a discharge valve after the reactor is heated to normal pressure, and discharging the materials to obtain the required polyester polyol. Sampling and analyzing acid ester, hydroxyl value, iodine value and molecular weight. The acid ester has a hydroxyl value of 75.6mgKOH/g, an iodine value of 0.153, a molecular weight of 2650g/mol and a temperature sensitivity index of 4.0 and is 1.358 mgKOH/g.
Example 10
2400g of methanol, 300g of toluene and 5.48g of ZM-701 were put into a reactor, and the temperature was raised to 45 ℃ with stirring. 90.97g of catalyst SO were added to the reactor4 2-/ZrO2676g of 2-pentene-1, 5-diacid and 633.6g of glutaric acid are added, stirring and dissolving are carried out, temperature rising is carried out simultaneously, the temperature is raised to 50 ℃ within 15min, in the process of temperature rising, dibasic acid and methanol start to react, water generated by the reaction leaves a reactor through an azeotrope formed by the dibasic acid and methylbenzene and part of the methanol, the water enters a rectifying tower arranged at the top of the reactor for separation, the methanol slides out from the top of the tower and flows back to the reactor, the azeotrope of the methylbenzene and the water is distilled out from the bottom of the tower, the water is separated, and the methylbenzene flows back to the reactor. The reaction was continued at 50 ℃ for 2h until no water was formed. Separating to remove the solid catalyst, heating the liquid material to 115 ℃, and distilling to remove the toluene in the system.
Adding the liquid product of the methyl diacid obtained from the esterification reaction into another reactor while the liquid product is hot, adding 1228.5g of diethylene glycol into the reactor under the condition of stirring, and adding 76.14mg of catalyst GeO2Heating to 120 deg.C, performing ester exchange reaction at 120 deg.C for 10 hr to obtain methanolAnd (5) separating and removing by using a distillation tower. When no methanol is generated, the oligomer of diacid and diol is obtained.
Vacuumizing the reactor, keeping the pressure of the reactor lower than 2kPa, gradually heating to 245 ℃ at the speed of 2 ℃/min, and reacting for 6h at constant temperature. Slowly introducing N into the reactor2And simultaneously closing the vacuum system, opening a discharge valve after the reactor is heated to normal pressure, and discharging the materials to obtain the required polyester polyol. Sampling and analyzing acid ester, hydroxyl value, iodine value and molecular weight. The acid ester has the advantages of 2.394mgKOH/g, 50.2mgKOH/g hydroxyl value, 0.158 iodine value, 11283g/mol molecular weight and 4.4 temperature sensitivity index.
Example 11
2080g of methanol, 300g of toluene and 6.83g of p-hydroxyanisole were introduced into a reactor, and the temperature was raised to 45 ℃ with stirring. 59.13g of catalyst SO were charged to the reactor4 2-/ZrO2609.12g of 3-methyl-2-pentene-1, 5-diacid and 761.64g of glutaric acid are added, stirring and dissolving are carried out, temperature rising is carried out simultaneously, the temperature rises to 60 ℃ within 15min, during the temperature rising process, dibasic acid and methanol start to react, water generated by the reaction leaves a reactor through an azeotrope formed by the water and toluene and part of methanol, the water enters a rectifying tower arranged at the top of the reactor for separation, the methanol slides out from the top of the tower and flows back to the reactor, the azeotrope of the toluene and the water is distilled out from the bottom of the tower and enters a water separator, water is separated, and the toluene flows back to the reactor. The reaction was continued at 60 ℃ for 5h until no water was formed. Separating to remove the solid catalyst, heating the liquid material to 115 ℃, and distilling to remove the toluene in the system.
Adding a liquid methyl diacid product obtained in the esterification reaction into another reactor while the liquid methyl diacid product is hot, adding 1543.5g of triethylene glycol into the reactor under the stirring condition, adding 131.14mg of catalyst antimony acetate, heating to 150 ℃, carrying out ester exchange reaction for 5h at 150 ℃, and separating and removing generated methanol from a distillation tower at the top of the reactor. When no methanol is generated, the oligomer of diacid and diol is obtained.
Vacuumizing the reactor, keeping the pressure of the reactor lower than 2kPa, gradually heating to 260 ℃ at the speed of 2 ℃/min, and reacting for 9h at constant temperature. Slowly introducing N into the reactor2While the vacuum system is turned off to be reversedAnd opening a discharge valve after the reactor is heated to normal pressure, and discharging the materials to obtain the required polyester polyol. Sampling and analyzing acid ester, hydroxyl value, iodine value and molecular weight. The acid ester has a hydroxyl value of 65.44mgKOH/g, an iodine value of 0.087, a molecular weight of 8200g/mol and a temperature sensitivity index of 4.9 and is 2.246 mgKOH/g.
Example 12
1600g of methanol, 300g of toluene and 1.40g of ZM-701 were charged into a reactor, and the temperature was raised to 45 ℃ with stirring. 69.77g of catalyst SO were charged to the reactor4 2-/WO31300g of 2-hexene-1, 6-diacid is added, the temperature is raised while stirring and dissolving, the temperature is raised to 80 ℃ within 15min, in the process of raising the temperature, dibasic acid and methanol start to react, water generated by the reaction leaves the reactor through an azeotrope formed by the water and toluene and part of methanol, enters a rectifying tower arranged at the top of the reactor for separation, the methanol slides out from the top of the tower and flows back to the reactor, the azeotrope of the toluene and the water is distilled off from the bottom of the tower and enters a water separator, the water is separated, and the toluene flows back to the reactor. The reaction was continued at 80 ℃ for 8h until no water was formed. Separating to remove the solid catalyst, heating the liquid material to 115 ℃, and distilling to remove the toluene in the system.
Adding the liquid methyl diacid product obtained from the esterification reaction into another reactor while the liquid methyl diacid product is hot, adding 767.6g of 1, 3-propanediol into the reactor under the condition of stirring, and adding 423.86mg of TiO catalyst2/SiO2The temperature is raised to 190 ℃, the ester exchange reaction is carried out for 9h at 190 ℃, and the generated methanol is separated and removed from a distillation tower at the top of the reactor. When no methanol is generated, the oligomer of diacid and diol is obtained.
Vacuumizing the reactor, keeping the pressure of the reactor lower than 2kPa, gradually heating to 250 ℃ at the speed of 2 ℃/min, and reacting for 8 hours at constant temperature. Slowly introducing N into the reactor2And simultaneously closing the vacuum system, opening a discharge valve after the reactor is heated to normal pressure, and discharging the materials to obtain the required polyester polyol. Sampling and analyzing acid ester, hydroxyl value, iodine value and molecular weight. The acid ester has the advantages of 1.654mgKOH/g, 42.58mgKOH/g hydroxyl value, 0.087 iodine value, 8200g/mol molecular weight and 6.1 temperature sensitivity index.
Example 13
1120g of methanol, 300g of toluene and 1.49g of p-hydroxyanisole were put into a reactor, and the temperature was raised to 45 ℃ with stirring. 108.84g of catalyst SO were added to the reactor4 2-/WO3259.2g of 3-methyl-2-pentene-1, 5-diacid and 1197.2g of adipic acid are added, stirring and dissolving are carried out, the temperature is raised simultaneously, the temperature is raised to 65 ℃ within 15min, during the temperature raising process, the dibasic acid and the methanol start to react, water generated by the reaction leaves the reactor through an azeotrope formed by the water and the toluene and part of the methanol, the water enters a rectifying tower arranged at the top of the reactor for separation, the methanol slips out from the top of the tower and flows back to the reactor, the azeotrope of the toluene and the water is distilled out from the bottom of the tower and enters a water separator, the water is separated, and the toluene flows back to the reactor. The reaction was continued at 65 ℃ for 7.5h until no water had formed. Separating to remove the solid catalyst, heating the liquid material to 115 ℃, and distilling to remove the toluene in the system.
Adding the hot diacid methyl ester liquid product obtained from the esterification reaction into another reactor, adding 1125g of 1, 4-butanediol into the reactor under the stirring condition, and adding 51.63mg of catalyst of antimony acetate and TiO2/SiO2The temperature is raised to 125 ℃, the ester exchange reaction is carried out for 7h at the temperature of 125 ℃, and the generated methanol is separated and removed from a distillation tower at the top of the reactor. When no methanol is generated, the oligomer of diacid and diol is obtained.
Vacuumizing the reactor, keeping the pressure of the reactor lower than 2kPa, gradually heating to 235 ℃ at the speed of 2 ℃/min, and reacting for 4h at constant temperature. Slowly introducing N into the reactor2And simultaneously closing the vacuum system, opening a discharge valve after the reactor is heated to normal pressure, and discharging the materials to obtain the required polyester polyol. Sampling and analyzing acid ester, hydroxyl value, iodine value and molecular weight. The acid ester has a hydroxyl value of 45.12mgKOH/g, an iodine value of 0.114, a molecular weight of 9433g/mol and a temperature sensitivity index of 5.5 and is 1.802 mgKOH/g.
Example 14
2880g of methanol, 300g of toluene and 2.62g of p-hydroxyanisole were put into a reactor, and the temperature was raised to 45 ℃ with stirring. 39.50g of catalyst Nafion-H, 525.4g of 2, 4-hexadiene-1, 6-adipic acid and 919.8g of adipic acid are added into a reactor, stirred, dissolved and heated at the same time, the temperature is raised to 95 ℃ within 15min, dibasic acid and methanol start to react in the heating process, water generated by the reaction leaves the reactor through an azeotrope formed by the water and toluene and part of the methanol, the water and the methanol enter a rectifying tower arranged at the top of the reactor for separation, the methanol is discharged from the top of the tower and flows back to the reactor, the azeotrope of the toluene and the water is distilled from the bottom of the tower and enters a water separator, the water is separated, and the toluene flows back to the reactor. The reaction was continued at a constant temperature of 95 ℃ for 3h until no water was formed. Separating to remove the solid catalyst, heating the liquid material to 115 ℃, and distilling to remove the toluene in the system.
Adding the liquid methyl diacid product obtained from the esterification reaction into another reactor while the liquid methyl diacid product is hot, adding 998.1g of 1, 2-butanediol into the reactor under the condition of stirring, and adding 61.08mg of catalyst isopropyl titanate + GeO2The temperature is raised to 115 ℃, the ester exchange reaction is carried out for 4 hours at the temperature of 115 ℃, and the generated methanol is separated and removed from a distillation tower at the top of the reactor. When no methanol is generated, the oligomer of diacid and diol is obtained.
Vacuumizing the reactor, keeping the pressure of the reactor lower than 2kPa, gradually heating to 250 ℃ at the speed of 2 ℃/min, and reacting for 6h at constant temperature. Slowly introducing N into the reactor2And simultaneously closing the vacuum system, opening a discharge valve after the reactor is heated to normal pressure, and discharging the materials to obtain the required polyester polyol. Sampling and analyzing acid ester, hydroxyl value, iodine value and molecular weight. The acid ester has a hydroxyl value of 67.98mgKOH/g, an iodine value of 0.136, a molecular weight of 3883g/mol and a temperature sensitivity index of 5.1 of 2.098 mgKOH/g.
Example 15
2240g of methanol, 300g of toluene and 4.45g of methylhydroquinone were charged into the reactor, and the temperature was raised to 45 ℃ with stirring. 1.3g of catalyst SO was added to the reactor4 2-/W20O581300g of 2, 4-hexadiene-1, 6-adipic acid is added, stirring and dissolving are carried out, the temperature is raised at the same time, the temperature is raised to 75 ℃ within 15min, in the process of temperature rise, dibasic acid and methanol start to react, water generated in the reaction leaves the reactor through an azeotrope formed by the dibasic acid and toluene and part of methanol, the water enters a rectifying tower arranged at the top of the reactor to be separated, the methanol slips out from the top of the tower and flows back to the reactor, the azeotrope of the toluene and the water is distilled out from the bottom of the tower and enters the reactorWater separator to separate water and toluene reflux to the reactor. The reaction was continued at 75 ℃ for 5.5h until no water was formed. Separating to remove the solid catalyst, heating the liquid material to 115 ℃, and distilling to remove the toluene in the system.
Adding the liquid methyl diacid product obtained from the esterification reaction into another reactor while the liquid methyl diacid product is hot, adding 1025.55g of 1, 4-butanediol into the reactor under the stirring condition, and adding 151.16mg of catalyst Sb2O3+GeO2The temperature is raised to 140 ℃, the ester exchange reaction is carried out for 1h at 140 ℃, and the generated methanol is separated and removed from a distillation tower at the top of the reactor. When no methanol is generated, the oligomer of diacid and diol is obtained.
Vacuumizing the reactor, keeping the pressure of the reactor lower than 2kPa, gradually heating to 260 ℃ at the speed of 2 ℃/min, and reacting for 5.5h at constant temperature. Slowly introducing N into the reactor2And simultaneously closing the vacuum system, opening a discharge valve after the reactor is heated to normal pressure, and discharging the materials to obtain the required polyester polyol. Sampling and analyzing acid ester, hydroxyl value, iodine value and molecular weight. The acid ester has a hydroxyl value of 57.82mgKOH/g, an iodine value of 0.098, a molecular weight of 5733g/mol and a temperature sensitivity index of 7.0.
Example 16
2720g of methanol, 300g of toluene and 6.54g of ZM-701 were put into a reactor, and the temperature was raised to 45 ℃ with stirring. Adding 9.41g of catalyst Nafion-H into a reactor, adding 892.8g of 3-methyl-2-pentene-1, 5-diacid and 608g of pimelic acid, stirring, dissolving and heating at the same time, heating to 50 ℃ within 15min, wherein dibasic acid and methanol start to react in the heating process, water generated by the reaction leaves the reactor through an azeotrope formed by the toluene and part of the methanol, enters a rectifying tower arranged at the top of the reactor for separation, the methanol is discharged from the tower top and flows back to the reactor, the azeotrope of the toluene and the water is distilled from the tower bottom and enters a water separator, moisture is removed, and the toluene flows back to the reactor. The reaction was continued at 50 ℃ for 6.5h until no water was formed. Separating to remove the solid catalyst, heating the liquid material to 115 ℃, and distilling to remove the toluene in the system.
Adding the liquid product of the methyl diacid obtained from the esterification reaction into another reactor while the liquid product is hot804.8g of 1, 2-propanediol were added to the reactor with stirring, and 11.53mg of the catalyst n-butyl titanate + Sb were added2O3The temperature is raised to 185 ℃, the ester exchange reaction is carried out for 2h at 185 ℃, and the generated methanol is separated and removed from a distillation tower at the top of the reactor. When no methanol is generated, the oligomer of diacid and diol is obtained.
Vacuumizing the reactor, keeping the pressure of the reactor lower than 2kPa, gradually heating to 250 ℃ at the speed of 2 ℃/min, and reacting for 6.5h at constant temperature. Slowly introducing N into the reactor2And simultaneously closing the vacuum system, opening a discharge valve after the reactor is heated to normal pressure, and discharging the materials to obtain the required polyester polyol. Sampling and analyzing acid ester, hydroxyl value, iodine value and molecular weight. The acid ester has a hydroxyl value of 62.9mgKOH/g, an iodine value of 0.109, a molecular weight of 10667g/mol and a temperature sensitivity index of 6.1 and is 2.542 mgKOH/g.
The embodiments described above are described to facilitate an understanding and use of the invention by those skilled in the art. It will be readily apparent to those skilled in the art that various modifications to these embodiments may be made, and the generic principles described herein may be applied to other embodiments without the use of the inventive faculty. Therefore, the present invention is not limited to the above embodiments, and those skilled in the art should make improvements and modifications within the scope of the present invention based on the disclosure of the present invention.
Claims (10)
1. A method for synthesizing unsaturated fatty diacid polyester polyol is characterized by comprising the following steps:
(1) under the action of a solid acid esterification catalyst, carrying out esterification reaction on unsaturated fatty diacid and methanol to generate unsaturated fatty diacid dimethyl ester;
(2) after the esterification reaction is finished, separating unsaturated fatty diacid dimethyl ester from a solid acid esterification catalyst, sending the mixture into a polyol solution added with an ester exchange catalyst, stirring and mixing the mixture evenly, and heating the mixture to perform an ester exchange reaction to generate diacid diol ester;
(3) after the ester exchange reaction is finished, continuously heating and carrying out polycondensation reaction to obtain the target product.
2. The method for synthesizing unsaturated fatty diacid-based polyester polyol as claimed in claim 1, wherein in step (1), the unsaturated fatty diacid is one or more of 2-pentene-1, 5-diacid, 3-methyl-2-pentene-1, 5-diacid, 2-hexene-1, 6-diacid and 2, 4-hexadiene-1, 6-adipate.
3. The method for synthesizing unsaturated fatty diacid-based polyester polyol as claimed in claim 1, wherein in step (1), the solid acid esterification catalyst is perfluorosulfonic acid resin or sulfated metal oxide, wherein the sulfated metal oxide is SO4 2-/Al2O3、SO4 2-/ZrO2、SO4 2-/TiO2、SO4 2-/WO3、SO4 2-/W20O58、SO4 2-/NbxOyX is 1 or 2; y is 1,2, 3, 5.
4. The method for synthesizing unsaturated fatty diacid-based polyester polyol as claimed in claim 1, wherein in the step (1), the amount of methanol is 100-160% of the molar amount of the unsaturated fatty diacid, and the amount of the solid acid esterification catalyst is 0.1-8% of the mass of the unsaturated fatty diacid.
5. The method for synthesizing unsaturated fatty diacid-based polyester polyol as claimed in claim 1, wherein the esterification reaction is carried out at 50-100 ℃ for 1-8.5 h in step (1).
6. The method for synthesizing unsaturated fatty diacid polyester polyol as claimed in claim 1, wherein in the step (2), the polyol is one or more of ethylene glycol, diethylene glycol, triethylene glycol, 1, 2-propylene glycol, 1, 3-propylene glycol, 1, 2-butylene glycol and 1, 4-butylene glycol;
the ester exchange catalyst is Sb2O3Antimony acetate, GeO2N-butyl titanate, isopropyl titanate, TiO2/SiO2One or more of the compounds are combined, and the addition amount of the compound is 5ppm to 225ppm of the total mass of the unsaturated fatty diacid and the dihydric alcohol.
7. The method for synthesizing unsaturated fatty diacid-based polyester polyol as claimed in claim 1, wherein in the step (2), the molar ratio of the polyol to the unsaturated fatty diacid dimethyl ester is 1.25: 1-1.05: 1;
the temperature of the ester exchange reaction is 115-190 ℃, and the time is 1-10 h.
8. The method for synthesizing unsaturated fatty diacid-based polyester polyol as claimed in claim 1, wherein in the step (3), the temperature of the polycondensation reaction is 220-260 ℃ and the time is 2-10 h.
9. The method for synthesizing unsaturated fatty diacid-based polyester polyol as claimed in claim 1, wherein a stabilizer is added into the whole reaction system, wherein the stabilizer is one or more of hydroquinone, p-hydroxyanisole, 2, 5-di-tert-butylhydroquinone, 2-tert-butylhydroquinone, p-benzoquinone, methylhydroquinone and 2,2,6, 6-tetramethyl-4-hydroxypiperidine nitroxide radical, and the addition amount of the stabilizer is 0.03-1.2% of unsaturated fatty diacid.
10. An unsaturated fatty diacid-based polyester polyol synthesized by the synthesis method of any of claims 1-9.
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Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| AU4690579A (en) * | 1978-05-24 | 1979-11-29 | Imperial Chemical Industries Ltd. | Polyester polyols |
| CN104650325A (en) * | 2015-02-05 | 2015-05-27 | 浙江南益生物科技有限公司 | Novel polyester polyol and preparation method thereof |
| CN111234186A (en) * | 2020-01-14 | 2020-06-05 | 湖州欧美化学有限公司 | Polyester polyol for polyurethane adhesive, preparation method thereof and polyurethane adhesive |
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Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| AU4690579A (en) * | 1978-05-24 | 1979-11-29 | Imperial Chemical Industries Ltd. | Polyester polyols |
| CN104650325A (en) * | 2015-02-05 | 2015-05-27 | 浙江南益生物科技有限公司 | Novel polyester polyol and preparation method thereof |
| CN111234186A (en) * | 2020-01-14 | 2020-06-05 | 湖州欧美化学有限公司 | Polyester polyol for polyurethane adhesive, preparation method thereof and polyurethane adhesive |
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| Title |
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| 贺俊海: "混酸合成混酸二甲酯和聚酯多元醇的研究" * |
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